Water borne film-forming compositions

ABSTRACT

The present invention provides a film_forming composition comprising a particulate polymer or emulsified liquid pre-polymer, water and a coalescent aid comprising an ester having the formula RCOOX wherein R and X are independently hydrocarbyl or substituted hydrocarbyl, and at least one of R and X contain at least two unsaturated carbon-carbon bonds. The coalescent aid helps lower the minimum film formation temperature of low glass transition temperature coatings and high glass transition temperature coatings and allows optimum film formation at ambient temperatures. The coalescent aid of this coating composition is not volatile like conventional coalescent aids by rather remains part of the film and air oxidizes to cure the film. This coating composition also exhibits properties of adhesion and gloss superior to that of coating compositions containing conventional coalescent aids. Additionally, this coalescent aid can be made from natural or synthetic oils.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of application Ser. No.09/532,839, filed Mar. 21, 2000, which claims priority from applicationSer. No. 60/125,446, filed Mar. 22, 1999, the contents of which arehereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

[0002] This invention generally relates to water borne film-formingcompositions containing a polyunsaturated ester as a coalescent aid.

BACKGROUND OF THE INVENTION

[0003] Aqueous dispersions of particulate polymer or emulsified liquidpre-polymers for use as paints, sealants, caulks, adhesives or othercoatings are well-known, widely-used articles of commerce. Theeffectiveness of the dispersion in forming a film after the polymerdispersion has been deposited upon a surface depends upon the glasstransition temperature of the dispersed polymer and the temperature atwhich the film is allowed to dry. See, for example, Conn et al., U.S.Pat. No. 2,795,564 and Emmons et al., U.S. Pat. No. 4,131,580.

[0004] Coalescent aids have been used in such aqueous dispersions tosoften, i.e., plasticize, the particulate polymers and facilitate theformation of a continuous film with optimum film properties once thewater has evaporated. In addition to increasing the ease of filmformation, the coalescent aid also promotes subsequent improvements infilm properties by coalescing the particulate polymers and liquidpre-polymers and forming an integral film at ambient temperatures.Without the coalescent aid, the films may crack and fail to adhere tothe substrate surface when dry.

[0005] Coalescent aids are particularly helpful in assisting theformation of particulate polymer films possessing a high glasstransition temperature, that is, the temperature which defines howeasily the particles of the polymer diffuse at the temperature at whichthe film-forming composition is applied. The presence of coalescent aidsin a particulate polymer film having a high glass transition temperatureallows optimum film formation at ambient temperatures.

[0006] Various alcohol esters and ether alcohols have been proposed foruse as coalescent aids. For example, in U.S. Pat. No. 4,131,580 Emmonset al. disclose water-based coating compositions based on vinyl additionpolymers of monoethylenically unsaturated monomers which comprisedicyclopentenyl acrylate and/or dicyclopentenyl methacrylate as acoalescent aid. In U.S. Pat. No. 4,141,868, Emmons et al. suggestcertain ester-ether compounds be used instead. Two of the more widelyused coalescent aids are ethylene glycol monobutyl ether (EB, UnionCarbide) and 2,2,4-trimethyl-1,3 pentanediol monobutyrate (TEXANOL®,Eastman Kodak). While EB and TEXANOL® are useful in facilitating filmformation of particulate polymer coatings with high glass transitiontemperatures and are even useful in facilitating film formation ofparticulate polymer coatings with low glass transition temperatures ifthey are being applied at a temperature that is lower than ambienttemperature, they are relatively volatile and, as a result, arecurrently classified as VOCs (volatile organic compounds).

SUMMARY OF THE INVENTION

[0007] Among the objects of the invention is a coalescent aid for use ina water-borne film forming composition wherein the coalescent aid is notclassified as a volatile organic compound, but which, nevertheless, (i)exhibits favorable adhesion and gloss relative to water bornefilm-forming compositions containing conventional coalescent aids, (ii)exhibits favorable minimum film formation temperature of low glasstransition temperature films and high glass transition temperature filmsand (iii) allows optimum film formation at ambient temperatures.

[0008] Briefly, therefore, the present invention provides a film-formingcomposition comprising a continuous aqueous phase and a dispersed phase.The dispersed phase comprises (i) a particulate polymer or emulsifiedliquid prepolymer, and (ii) a coalescent aid comprising an ester havingthe formula RCOOX wherein R and X are independently hydrocarbyl orsubstituted hydrocarbyl and at least one of R and X comprises at leasttwo unsaturated carbon-carbon bonds. Other objects of the invention willbe in part apparent and in part pointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009]FIG. 1 is the MFFT (C) plot for FLEXBOND 325 as a function of %coalescent aids;

[0010]FIG. 2 is the MFFT (C) plot for UCAR 379 as a function of %coalescent aids;

[0011]FIG. 3 is the MFFT (C) plot for ACRONAL A846 as a function of %coalescent aids;

[0012]FIG. 4 is the MFFT (C) plot for UCAR 430 as a function of %coalescent aids;

[0013]FIG. 6 is the MFFT plot for UCAR 430 as a function of coalescentaids;

[0014]FIG. 7 is the MFFT plot for UCAR 430 as a function of coalescentaids;

[0015]FIG. 8 is the MFFT plot for ACRONAL A846 as a function ofcoalescent aids; and

[0016]FIG. 9 is the MFFT plot for ACRONAL A846 as a function ofcoalescent aids.

[0017] In FIGS. 1-4 and 6-9, X1, X2, X3, X4, EB, EB_X and EB+X have thefollowing meanings:

[0018] X1=Ethylene glycol soy oil ester,

[0019] X2=Propylene glycol soy oil ester,

[0020] X3=Diethylene glycol soy oil ester,

[0021] X4=Dipropylene glycol soy oil ester,

[0022] EB=Ethylene glycol monobutyl ether,

[0023] EB_X=derivatives and EB mixture 50:50, and

[0024] EB+X=derivatives and EB mixture 50:50.

[0025] FIGS. 1-4 and 6-9 are plots of minimum film formation temperatureas a function of % coalescent aid;

[0026]FIG. 5 is a plot of the evaporation rate of coalescent aid as afunction of time;

[0027]FIG. 10 is a plot of coating resistance and charge transferresistance as a function of dry time;

[0028]FIG. 11 is a plot of coating capacitance and associated doublelayer capacitance as a function of dry time;

[0029] FIGS. 12-19 are infrared spectra of soybean oil and variouscoalescent aids;

[0030] FIGS. 20-27 are ¹H-NMR spectra of soybean oil and variouscoalescent aids; and

[0031] FIGS. 28-32 are ¹³C-NMR spectra of soybean oil and variouscoalescent aids.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The water-borne film-forming compositions of the presentinvention generally contain a continuous aqueous phase and a dispersedfilm-forming phase. In general, they may be formulated to function as apaint, sealant, caulk, adhesive or other coating. Thus, thesefilm-forming compositions may have a wide range of viscosities, e.g.,from about 50 to about 10,000 centipoise; paints, sealants and similarcoatings typically have a viscosity from about 50 to about 10,000centipoise, caulks typically have a viscosity from about 5,000 to about50,000 centipoise, and adhesives typically have a viscosity from about50 to about 50,000 centipoise. In addition, adhesives are formulated forcohesive strength as well as good contact with the substrate upon whichthe film-forming composition is deposited.

[0033] The continuous aqueous phase generally comprises at least about10 wt % water with the amount of water depending upon the application.For example, paints, sealants and similar coating compositions willgenerally have at least about 10 wt % water and typically will containabout 20 wt % to about 80 wt % water with differing amounts being usedfor textured, high gloss, semi-gloss, flat, etc. coatings. Caulks willgenerally have at least about 10 wt % water and typically will containabout 10 wt % to about 25 wt % water with differing amounts being usedfor different caulk applications. Adhesives will generally range fromabout 10 wt % to about 80 wt % water and typically will contain about 40wt % to about 60 wt % water with differing amounts being used fordifferent adhesive applications.

[0034] The continuous aqueous phase may optionally include one or morewater-soluble organic solvents, i.e., substituted hydrocarbon solvents.For example, modest amounts of ethylene glycol (e.g., 3-5 wt. %) oranother glycol may be included for freeze-thaw protection. In general,however, the proportion of water-soluble organic solvents is preferablyminimized; that is, the continuous aqueous phase preferably containsless than about 20 wt. % organic solvent, more preferably less thanabout 10 wt. % organic solvent, and still more preferably less thanabout 5 wt. % organic solvent, based upon the weight of the continuousaqueous phase and exclusive of any amount which may be present in amicelle or other dispersed phase or material.

[0035] The dispersed phase comprises a (i) particulate polymer or anemulsified liquid pre-polymer, (ii) a coalescent aid and, optionally,(iii) one or more additives. In general, the dispersed phase constitutesno more than about 90 wt % with the amount of dispersed phase dependingupon the application. For example, paints, sealants and similar coatingcompositions will generally have no more than about 90 wt % dispersedphase and typically will contain about 20 wt % to about 80 wt %dispersed phase with differing amounts being used for textured, highgloss, semi-gloss, flat, etc. coatings. Caulks will generally have nomore than about 90 wt % dispersed phase and typically will contain about75 wt % to about 90 wt % dispersed phase with differing amounts beingused for different caulk applications. Adhesives will generally rangefrom about 20 wt % to about 90 wt % dispersed phase and typically willcontain about 40 wt % to about 60 wt % dispersed phase with differingamounts being used for different adhesive applications.

[0036] In general, the particulate polymer or emulsified liquidpre-polymer is insoluble in the aqueous phase and is otherwise suitablefor use in water borne film-forming compositions. Because theparticulate polymer or emulsified liquid pre-polymer is the componentwhich coalesces to form the desired film, the film-forming compositionpreferably comprises at least about 10 wt. %, more preferably at leastabout 15 wt. %, and depending for some applications at least about 20wt. % of a coalescible particulate polymer or emulsified liquidpre-polymer.

[0037] Preferred particulate polymers are generally high molecularweight (e.g, greater than about 60,000 for latex), crosslinkable,polymer particles. For example, they may be either of the addition type,in particular a polymer or copolymer of one or more α,β-ethylenicallyunsaturated monomers, or of the condensation type, for example, apolyester or a polyamide. Suitable particulate polymers of the additiontype include the polymerization and copolymerization products ofstyrene, vinyl acetate, vinyl toluene, vinyl chloride, vinylidenechloride, butadiene, vinyl hydrocarbons, acrylonitrile, acrylates, andmethacrylate containing monomers. Suitable condensation type particulatepolymers include epoxy, urethane, hydrocarbon, silicone, nitrocellulose,polyester, and alkyd polymers. Preferred particulate polymers includeacrylate, methacrylate, styrene and vinyl acetate. Examples of preferredparticulate polymers include the polymerizates or copolymerizates of oneor more of the following: alkyl acrylates such as ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, as well as other alkyl acrylates, alkylmethacrylates, styrene and vinyl acetate.

[0038] In general, smaller particulate polymers are more readilycoalesced than larger particulate polymers. Accordingly, preferredparticulate polymers generally have a size of about 3 micrometers orless. For example, for latex resins, approximately 90 wt. % of the latexparticles will have a size less than about 0.2 micrometers.

[0039] Preferred emulsified liquid pre-polymers include alkyds, epoxies,nitrocellulose, and urethanes.

[0040] The coalescent aid of the present invention preferably comprisesan ester having the formula

RCOOX

[0041] wherein

[0042] R is hydrocarbyl or substituted hydrocarbyl,

[0043] X is hydrocarbyl or substituted hydrocarbyl, and

[0044] at least one of R and X contains two or more aliphaticunsaturated carbon-carbon bonds (hereinafter “polyunsaturated”).

[0045] Preferably, R contains about 1 to about 30 carbon atoms, morepreferably about 9 to about 25 carbon atoms, and still more preferablyabout 15 to about 23 carbon atoms, X contains about 1 to about 30 carbonatoms, more preferably about 1 to about 18 carbon atoms, and still morepreferably about 1 to about 6 atoms, and R and X in combination containno more than about 35 carbon atoms, and more preferably, R and X, incombination, contain no more than about 30 carbon atoms. In addition, atleast one of R and X preferably contains a conjugated double or triplecarbon-carbon bond (i.e., two or more carbon-carbon double or triplebonds which alternate with carbon-carbon single bonds). For example, theunsaturation may take the form of two conjugated double bonds, aconjugated double bond and triple bond or two conjugated triple bonds.

[0046] While the carbon-carbon polyunsaturation may be provided in R orX, it is generally preferred that it be provided at the tail of theester, i.e., in R. Thus, R is preferably hydrocarbyl or substitutedhydrocarbyl possessing at least two aliphatic unsaturated carbon-carbonbonds, more preferably in conjugation, with R preferably comprisingabout 5 to about 25 carbon, more preferably about 9 to about 25 carbonatoms, and still more preferably about 11 to about 23 carbon atoms. If Ris substituted hydrocarbyl, it is preferably substituted with ketone,amide, ester, alcohol, urea, urethane, nitrile functionalities; silyland amine functionalities are preferably avoided and alcohols arepreferably avoided if the number of carbon atoms is less than about 10.

[0047] Optionally, the head of the ester, i.e., X, may bepolyunsaturated instead of the tail of the ester. In this instance, X ispreferably hydrocarbyl or substituted hydrocarbyl possessing at leasttwo aliphatic unsaturated carbon-carbon bonds, more preferably inconjugation with X preferably comprising about 5 to about 30 carbon,more preferably about 5 to about 25 carbon atoms, and still morepreferably about 5 to about 24 carbon atoms.

[0048] If R is polyunsaturated, X may optionally contain one or moredegrees of carbon-carbon unsaturation. Stated another way, X may behydrocarbyl or substituted hydrocarbyl optionally possessing one or moredegrees of carbon-carbon unsaturation. As with R, X may optionallycontain at least 2 degrees of carbon-carbon unsaturation with the 2degrees of carbon-carbon unsaturation optionally being in conjugation.In one embodiment of the present invention, for example, X is X′—OHwherein X′ is a hydrocarbyl or substituted hydrocarbyl radicalcomprising about 1 to about 8 carbon atoms. Preferably, X′ comprisesabout 2 to about 6 carbon atoms and, in one embodiment X′ possesses atleast one degree of unsaturation. If X or X′ is substituted hydrocarbyl,it is preferably substituted with ketone, amide, ester, alcohol, urea,urethane, nitrile functionalities; silyl and amine functionalities arepreferably avoided.

[0049] The polyunsaturated ester of the present invention is preferablysufficiently involatile to avoid categorization as a Volatile OrganicCompound by the United States Environmental Protection Agency. In oneembodiment of the present invention, the coalescent aid is a singleester. In another embodiment of the present invention, the coalescentaid comprises a mixture of esters with at least one of the esters beinga polyunsaturate. In a third embodiment, the coalescent aid comprises apolyunsaturated ester with a conventional coalescent aid such asethylene glycol monobutyl ether (EB, Union Carbide) or2,2,4-trimethyl-1,3 pentanediol monobutyrate (TEXANOL®, Eastman Kodak).Where composition(s) other than polyunsaturated esters are also used asa coalescent aid, it is generally preferred that the polyunsaturatedester comprise at least about 5 wt. %, more preferably at least about 10wt. %, still more preferably at least about 25 wt. %, still morepreferably at least about 50 wt. %, and still more preferably at leastabout 75 wt. %, based upon the total combined weights of thecompositions used as coalescent aids.

[0050] The polyunsaturated ester of the present invention may be derivedfrom a natural, genetically engineered or synthetic material such as anoil, fat, lecithin or petroleum product. In a preferred embodiment, thecoalescent aid comprises a polyunsaturated ester derived from an oil ofplant or animal origin (including oils obtained from geneticallyengineered species), such as canola, linseed, soybean, or anothernaturally occurring oil such as one identified in Table I. Examples ofpreferred polyunsaturated esters include methyl ester, ethylene glycolmonoester, diethylene glycol monoester, propylene glycol monoester, anddipropylene glycol monoester derived from the fatty acids of these oils.TABLE I VEGETABLE OIL AVERAGE FATTY ACID AS PERCENT OF TOTAL FATTY ACIDNumber of Carbon Atoms * 6 10 12 14 16 18 18 18 18 16 18 22 20-22 20-24Number of Double Bonds 0 0 0 0 0 0 1 2 3 1 1 1 ** 3 Castor 85 1.0 2.02.0 5.0 90.0 Corn 124 13.0 4.0 29.0 54.0 Cottonseed 107 22.0 2.0 21.054.0 Crambe 94 3.0 2.0 18.0 10.0 5.0 56.0 3.0 2.0 Linseed 185 6.0 4.020.0 17.0 53.0 Mustard 120 2.0 24.0 20.0 6.0 43.0 5.0 Olive 80 8.0 2.082.0 8.0 Oiticica¹ 150 7.0 6.0 5.0 Peanut 90 7.0 6.0 60.0 22.0 5.0Rapeseed 101 2.0 2.0 16.0 16.0 8.0 45.0 6.0 4.0 Rice Bran 102 17.0 1.047.0 35.0 Safflower 141 6.0 2.0 13.0 79.0 Sardine, Pilchard 190 14.0 3.010.0 15.0 12.0 41.0 Sesame 110 9.0 4.0 46.0 41.0 Soybean 130 8.0 6.028.0 50.0 8.0 Sunflower 139 6.0 2.0 26.0 66.0 Tung (Regular)² 165 4.01.0 5.0 8.0 Tung (African)³ 160 4.0 1.0 9.0 15.0 Walnut (English) 1509.0 1.0 16.0 60.0 13.0

[0051] The fatty acid ester glycols may be prepared bytransesterification reactions between various glycols and fatty acidsfrom soybean and other oils of plant or animal origin in the presence ofa catalyst. Suitable catalysts include bases such as lithium hydroxide,tin oxides, tin catalysts, and calcium oxide with the reactiontemperature generally being about 100 to about 200° C. In a preferredembodiment, the glycol used in the reaction is ethylene glycol,propylene glycol, diethylene glycol or dipropylene glycol with thereaction being carried out with about 6 moles of glycol per mole ofsoybean oil in the presence of a basic catalyst at a temperature ofabout 190° C. under nitrogen atmosphere. After reaction, the excessglycol is extracted with water several times. The soy oil ester isextracted with ethyl ether and dried, for example, with magnesiumsulfate. Then the ethyl ether is distilled off. The reaction equation isgiven below.

[0052] where R is unsaturated hydrocarbon chain having 17 carbons

[0053] R′ is a group of the formula

—C₂H₄—for ethylene glycol

—C₃H₆—for propylene glycol

—C₂H₄O—C₂H₄—for diethylene glycol

—C₃H₆O—C₃H₆—for dipropylene glycol

[0054] The amount of coalescent aid needed to assist in film formationdepends on the viscosity of the film-forming composition, thetemperature at which the composition is being applied, the glasstransition temperature of the film-former, and the minimum filmformation temperature of the film-former. In general, the amount ofcoalescent will be proportional to the amount and type of resin usedwith ratios in the range of about 0.1 wt % to about 50 wt. % (based uponthe weight of the dry resin), typically in the 1 wt. % to about 4 wt. %range (based upon the weight of the dry resin).

[0055] Any coalescent aid which remains in the film will act as aplasticizer, keeping the glass transition temperature low unless it haspolyunsaturation which will allow it to be air oxidized and oligomerizedwhich results in the coalescent aid becoming more of a resin and less ofa plasticizer. Thus, the glass transition temperature is in partrecovered. In general, the greater degree of unsaturation of thecoalescent aid the more glass transition temperature recovery can beexpected. Where a mixture of materials are used as the coalescent aid,therefore, it is generally preferred that the polyunsaturated acid(s)comprise at least about 5 wt. %, more preferably at least about 25 wt.%, still more preferably at least about 40 wt. % and still morepreferably at least about 50 wt. % of the coalescent aid.

[0056] Trace amounts of the polyunsaturated ester coalescent aid of thepresent invention may be dissolved in the continuous aqueous phase; thatis, preferably less than about 10 wt. %, more preferably less than 5 wt.%, still more preferably less than 1 wt. %, and for some embodimentsstill more preferably less than about 0.5 wt. % of the polyunsaturatedester is dissolved in the continuous aqueous phase, based upon theweight of the continuous aqueous phase. The predominant proportion ofthe polyunsaturated ester coalescent aid is thus preferably dissolved inthe dispersed particulate polymer or liquid pre-polymer. Preferably atleast 80 wt. %, more preferably at least 90 wt. %, more preferably atleast 95 wt. %, and still more preferably at least 99 wt. % of thepolyunsaturated ester coalescent aid is dissolved in the dispersedparticulate polymer or liquid pre-polymer. Depending upon the type andamount of surfactants included in the film-forming composition, arelatively small fraction of the polyunsaturated ester coalescent aidmay additionally be emulsified in the continuous aqueous phase and foundin micelles along with surfactant.

[0057] The film-forming composition of the present invention may alsocontain various conventional additives which may be in the dispersedand/or continuous phases. Such additives include thickening agents suchas carboxymethylcellulose sold by Aquilon under the trade designationNATRASOL 250 and thickeners sold under the trade designation M-P-A 1075by Rheox, pH modifiers such as ammonium hydroxide and N,N-dimethylethanolamine, defoaming agents such as mineral oil or silicone oils,wetting agents such as a nonionic surfactant sold by AKZO under thetrade designation INTERWET 43 and a nonionic surfactant sold by Rohm &Haas under the trade designation Triton X100, algicides such asorganotin compounds and tetrachloroisophthalonitrile, fungicides such astributyl tin oxide, and 3-iodo-2-propynyl butyl carbamate, dispersantssuch as lecithin and an anionic dispersant sold under the tradedesignation BUSPERSE 39 by Buckman, ultraviolet inhibitors such as abenztriazol UV inhibitor sold under the trade designation TINUVIN 328 byCiba-Geigy and a hindered amine UV inhibitor sold under the tradedesignation by TINUVIN 123 by Ciba-Geigy, flow and leveling agents suchas a polyacrylate sold under the trade designation BYK 354 by BYK-Chemieand a polysiloxane copolymer sold under the trade designation BYK 310 byBYK-Chemie, flash rust inhibitors such as an inhibitor sold under thetrade designation RAYBO 63 by Raybo or a barium metaborate rustinhibitor sold under the trade designation BUSAN 11 M1 by Buckman, andfreeze/thaw inhibitors such as ethylene glycol. Additional additivesinclude driers such as cobalt driers carboxylate salts (0.0 to 0.15 wt.% Co based on the coalescent aid) and manganese driers carboxylate salts(0.0 to 0.15 wt. % based on the coalescent aid), accelerators such as1,10-phenanthroline (0 to 0.2 % based on the coalescent aid) and2,2-bipyridine (0 to 0.2 % based on the coalescent aid), andanti-skinning agents such as butanone oxime (0−1 lb/100 galformulation). When present and depending upon the application for thefilm-forming composition, these additives will generally not constitutemore than about 10 wt. % of the film-forming composition and willtypically constitute about 3 wt. % to about 10 wt. % of the film-formingcomposition.

[0058] The film-forming composition is formed by conventional methodsused to prepare paints, adhesives, except that the polyunsaturated esterof the present invention is substituted, at least in part, for aconventional coalescent aid. The resulting film-forming composition caneasily be applied conventionally using a brush, roller, or like meansand requires no unusual methods of drying to form the desired film.Thus, films formed from the composition of the present invention may bedried under ambient conditions. Furthermore, the film-formingcomposition may be applied to a variety of materials.

[0059] Definitions

[0060] As used herein, the term “hydrocarbyl” shall mean a radicalconsisting exclusively of carbon and hydrogen. The hydrocarbyl may bebranched or unbranched, saturated or unsaturated. Suitable hydrocarbylmoieties include alkyl, alkenyl, alkynyl, and aryl moieties. They alsoinclude alkyl, alkenyl, alkynyl, and aryl moieties substituted withother saturated or unsaturated hydrocarbyl moieties such as alkaryl,alkenaryl and alkynaryl. Preferably, the hydrocarbyl does not include anaryl moiety and except as otherwise indicated herein, the hydrocarbylmoieties preferably comprises up to about 25 carbon atoms.

[0061] The aryl moieties described herein contain from 6 to 20 carbonatoms and include phenyl. They may be hydrocarbyl substituted with thevarious substituents defined herein. Phenyl is the more preferred aryl.

[0062] The term “substituted hydrocarbyl” shall mean a hydrocarbylradical wherein at least one hydrogen atom has been substituted with anatom other than hydrogen or carbon, including moieties in which a carbonchain atom is substituted with a hetero atom such as nitrogen, oxygen,silicon, phosphorous, boron, sulfur, or a halogen atom. Thesesubstituents include hydroxy; lower alkoxy such as methoxy, ethoxy,butoxy; halogen such as chloro or fluoro; ethers; esters; heteroarylsuch as furyl or thienyl; alkanoxy; acyl; acyloxy; nitro; amino; andamido. In general, however, amines and silyl radicals are preferablyexcluded.

[0063] The acyl moieties and the acyloxy moieties described hereincontain hydrocarbyl, substituted hydrocarbyl or heteroaryl moieties. Ingeneral, they have the formulas —C(O)G and —OC(O)G, respectively,wherein G is substituted or unsubstituted hydrocarbyl, hydrocarbyloxy,hydrocarbylamino, hydrocarbylthio or heteroaryl.

[0064] This invention will be further illustrated by the followingExamples although it will be understood that these Examples are includedmerely for purposes of illustration and are not intended to limit thescope of the invention.

EXAMPLES

[0065] Test Procedures

[0066] The following test procedures were used to generate the datareported in the examples below:

[0067] Minimum Film Formation Temperature Measurement

[0068] The method used for measuring MFFT followed ASTM Method D2354-68.Minimum film formation temperatures for ten different coalescent aidformulated latexes were measured. Four replicate measurements wereperformed for the same latex and were then averaged.

[0069] Blocking Resistance Testing

[0070] The procedure employed to evaluate block resistance followed ASTMMethod D4946-89. A 6 mil thick film of latex was drawn down on a Lenetachart and dried for 7 days at room temperature. The dried films were cutinto squares ˜1.5×1.5 inch² and the squares were placed together withface to face contacted each other. The face-to-face specimens wereplaced in a 35° C. oven on the flat aluminum tray. A 1000 kg weight on aNo. 8 stopper were placed on the specimens to yield a pressure of about1.8 psi (127 g/cm²). After exactly 30 min, the stopper and weight wereremoved. The sample was allowed to cool for 30 min at room temperaturebefore determining the block resistance according to the followingscale: 10 no tack 9 trace tack 8 very slight tack 7 very slight toslight tack 6 slight tack 5 moderate tack 4 very tacky, no seal 3  5-25%seal 2 25-50% seal 1 50-75% seal 0 75-100% seal

[0071] Adhesion Testing

[0072] The method used to for determining adhesion followed ASTM MethodD3359-92a. A 6 mil wet film thickness of latex was drawn down on analuminum panel and dried for 7 days at room temperature. After drying,an area was selected that was free of blemishes and minor surfaceimperfections. Eleven cuts in each direction, orthogonal, were madethrough the film to the substrate in one steady motion using sufficientpressure on the cutting tool to have the cutting edge reach thesubstrate. Make all cuts about ¾ inch (20 mm). Place the center of thetape over the grid and in the area of the grid smooth into place by afinger. To ensure good contact with the film, rub the tape firmly withthe eraser. The opacity change of the tape was a useful indication ofwhen good contact has been made. Within 90 sec of application, removethe tape by seizing the free end and rapidly pull back upon itself at anangle of approximately 1800. Inspect the grid area for removal ofcoating from the substrate. Rate the adhesion in accordance with thefollowing scale:

[0073] 5B The edges of the cuts are completely smooth; none of thesquares of the lattice is detached.

[0074] 4B Small flakes of the coating are detached at intersections;less than 5% of the area is affected.

[0075] 3B Small flakes of the coating are detached along edges and atintersections of cuts. The area affected is 5-15% of the lattice.

[0076] 2B The coating has flaked along the edges and on parts of thesquares.

[0077] The area affected is 15-35% of the lattice.

[0078] 1B The coating has flaked along the edges of cuts in large ribbonand whole squares have detached. The area affected is 35-65% of thelattice.

[0079] 0B Flaking and detachment worse than grade 1B.

[0080] Freeze-Thaw and Thermal Stability

[0081] Three, 500 grams cans of paint had been prepared for each systembeing investigated. One was for freeze-thaw stability test, one forthermal stability test and the other one for control. The controlsamples were stored at room temperature.

[0082] For thermal stability testing, paint cans were put in oven at 50°C. for 17 hours, then was taken out to cool at room temperature for 7hours. This is a cycles of testing. Repeat testing for at least 5 cyclesand observed a physical appearance of paints in cans. Gloss and hidingpower were measured and compared with those from control.

[0083] For freeze-thaw stability testing, one cycle composes of 17 hoursof freezing in a refrigerator at −8° C. and 7 hours of thawing at roomtemperature. At least 5 cycles had been taken. The physical appearanceof paints were observed. Gloss and hiding power were measured andcompared with those from control.

[0084] Gloss and Hiding Power

[0085] Each paint formulation was drawn down onto a Lenetta chart withfilm thickness of 3 mils, and let dry at room temperature for two daysbefore gloss (@60°) and hiding power measurement would be taken byglossmeter and color computer, respectively.

[0086] Scrub Resistance Testing

[0087] Each paint formulation was drawn down onto a plastic panel with 6mil draw down bar and let dry at room temperature for 7 days beforetesting. The testing including scrub media preparation was by the methoddescribed in ASTM D 2486-89.

[0088] Pencil Hardness Testing

[0089] The method used for determining hardness followed ASTM MethodD3363-92a. A 6 mil thickness film of latex was drawn down on an aluminumpanel and dried for 7 days at room temperature. After drying, an areawas selected that was free of blemishes and minor surface imperfections.The pencils was prepared by polishing the tip of the pencil in circularmotion to get a sharp edge. The panel was placed on a firm horizontalsurface. The pencil was held firmly against the film at a 45° angle(point away from operator) and pushed away from the operator in a ¼ instroke. The pencil number that does not cut into or gauge the paint filmwas reported.

[0090] Evaporation Rate

[0091] Three samples of each coalescent aid was weighed into aluminumpans. All test samples were kept at room temperature. The percentage ofweight loss of each coalescent aid was measured as a function of time.

[0092] Surface Tension

[0093] Surface tension was determined by the ring method tensiometeraccording to ASTM D 1331-89.

[0094] Hydrophilic Lipophilic Balance

[0095] Hydrophilic lipophilic balance (HLB) values were calculated fromEquation propynyl 1 based on ethylene oxide moiety in the molecule.$\begin{matrix}{{HLB} = \frac{\% \quad {{wt}.\quad {of}}\quad {ethylene}\quad {oxide}\quad {in}\quad {the}\quad {molecule}}{5}} & {{Equation}\quad 1}\end{matrix}$

[0096] Solubility Parameters

[0097] Solubility parameter values were calculated according to theHansen Method from the Handbook of Solubility Parameters.

[0098] Density

[0099] Density was determined according to ASTM D-1475.

[0100]¹³C NMR Spectra

[0101]¹³C NMR spectra were determined without solvent added at roomtemperature in 5-mm inner-diameter tubes.

[0102]¹H NMR Spectra

[0103]¹H NMR spectra were operated with neat liquid reaction products.

Example 1

[0104] Coalescent efficiency using a low Tg latex polymer with varioussoybean oil esters.

[0105] Master batch formulation for MFFT testing of vinyl acetate latex,FLEXBOND 325, and vinyl acrylic latex, UCAR 379G is given in the Tablebelow. Formulation for studying MFFT for low Tg latex polymersformulation solid content lb. gal. lb. gal. H2O 286.35 34.38 0.00 0.00PG 43.20 4.99 0.00 0.00 X-102 1.98 0.22 1.98 0.22 RM825 1.82 0.21 0.460.05 WET260 0.87 0.10 0.87 0.10 AMP95 1.98 0.25 0.00 0.00 low Tg resins430.22 47.54 236.62 24.44 DREWPLUS 493 2.38 0.32 0.36 0.13 H2O 99.8811.99 0.00 0.00 Total 868.69 100.00 240.29 24.94 wt/gal 8.69 % sol/wt27.66 % sol/vol. 24.94

[0106] To 50 grams portion of master batch was added the coalescent aidsat the following levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%).The samples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

[0107] As illustrated by FIG. 1, all new soy oil glycol ester coalescentaids of this invention show a potential in lowering the minimum filmformation temperature of latex polymer, FLEXBOND 325 similar tocommercial coalescent aids TEXANOL® and EB.

[0108] As shown in FIG. 2, all new soy oil glycol ester coalescent aidsof this invention show a capability in lowering the minimum filmformation temperature of latex polymer, UCAR 379G, better than thecommercial coalescent aid TEXANOL®, and also give a similar trend to thecommercial coalescent aid EB.

Example 2

[0109] Coalescent efficiency using a high Tg latex polymer with varioussoybean oil glycol esters.

[0110] Master batch formulation for MFFT testing of high Tg acryliclatex, ACRONAL A846, is given in the Table below. Formulation forstudying MFFT for ACRONAL A846 formulation solid content lb. gal. lb.gal. H2O 278.29 33.41 0.00 0.00 PG 42.40 4.90 0.00 0.00 X-102 5.09 0.575.09 0.57 RM825 3.85 0.44 0.96 0.10 WET kl245 7.71 0.89 7.71 0.89 AMP950.00 0.00 0.00 0.00 Acronal486 418.60 47.84 209.30 22.82 DREWPLUS 2.160.29 0.32 0.12 H2O 97.13 11.66 0.00 0.00 Total 855.23 100.00 223.3824.50 wt/gal 8.55 % sol/wt 26.12 % sol/vol. 24.50

[0111] To 50 grams portion of master batch was added the coalescent aidsat the following levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%).The samples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

[0112] As illustrated by FIG. 3, all new soy oil glycol ester coalescentaids of this invention show a capability in lowering the minimum filmformation temperature of high Tg acrylic latex polymer, ACRONAL A846,better than the commercial coalescent aid EB, and also give a similartrend to the commercial coalescent aid TEXANOL® at every level ofcoalescent aids added.

[0113] Master batch formulation for MFFT testing of high Tgpolystyrene/polymethyl methacrylate latex, UCAR 430, is given in theTable below. Formulation for studying MFFT for UCAR 430 formulationsolid content lb. gal. lb. gal. H2O 288.56 34.64 0.00 0.00 PG 43.96 5.080.00 0.00 X-102 5.28 0.59 5.28 0.59 RM825 4.00 0.46 1.00 0.10 WET kl2457.99 0.92 7.99 0.92 AMP95 0.00 0.00 0.00 0.00 UCAR430 434.03 49.89195.31 21.23 DREWPLUS 2.24 0.30 0.34 0.12 H2O 67.62 8.12 0.00 0.00 Total853.68 100.00 209.92 22.97 wt/gal 8.54 % sol/wt 24.59 % sol/vol. 22.97

[0114] To 50 gram portion of master batch was added the coalescent aidsat the following levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%).The samples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

[0115] As shown in FIG. 4, all new soy oil glycol ester coalescent aidsof this invention show a capability in lowering the minimum filmformation temperature of high Tg PS/PMMA latex polymer, UCAR 430, betterthan the commercial coalescent aid EB, and also give a similar trend tothe commercial coalescent aid TEXANOL® at every level of coalescent aidsadded.

Example3

[0116] Physical properties of paint formulations with a low Tg latexpolymer with ethylene glycol soybean oil esters and TEXANOL®.

[0117] Semigloss and flat paint formulations of low Tg , vinyl acetatelatex, FLEXBOND 325, have been prepared for physical testing. Theformulations with TEXANOL® are given in the Tables below. GLOSSPAINT/FLEXBOND325/TEXANOL ® formulation lb. gal H2O 50.58 52.58 PG 58.286.74 X-102 2.01 0.22 RM825 15.70 1.80 TAMOL850 8.29 0.84 WET260 4.510.52 AMP95 3.62 0.46 TP-900 224.91 6.75 ATOMITE 73.46 3.25 FXBD325582.93 64.06 TEXANOL ® 18.92 2.39 DREWPLUS 1.91 0.26 H2O 55.19 6.62Total 1100.30 100.00 wt/gal 11.00 % sol/wt 57.46 % sol/vol. 44.39 % PVC22.55

[0118] FLAT PAINT/FLEXBOND325/TEXANOL ® formulation lb. gal H2O 141.8317.03 PG 43.31 5.01 X-102 2.17 0.24 RM825 20.77 2.39 TAMOL850 18.08 1.83WET260 4.85 0.56 AMP95 2.17 0.28 TP-900 241.98 7.27 ATOMITE 194.88 8.63FXBD325 433.07 47.59 TEXANOL ® 14.07 1.78 DREWPLUS 2.06 0.27 H2O 59.377.13 Total 1178.61 100.00 wt/gal 11.79 % sol/wt 58.80 % sol/vol. 42.22 %PVC 37.66

[0119] The formulations with ethylene glycol derivative soybean oilglycol esters are given in the Tables below. GLOSSPAINT/FLEXBOND325/SYNTHETIC COALESCENT AID formulation (by weight)formulation (by volume) lb. gal. H2O 77.67 9.32 PG 56.05 6.48 X-102 1.840.20 RM825 17.42 2.00 TAMOL850 7.97 0.81 WET260 4.34 0.50 AMP95 4.240.54 TP-900 216.28 6.49 ATOMITE 70.64 3.13 FXBD325 560.56 61.60EG-DERIV(X1) 18.19 2.30 DREWPLUS 1.84 0.25 H2O 53.07 6.37 Total 1090.09100.00 wt/gal 10.90 % sol/wt 55.81 % sol/vol. 42.73 % PVC 22.52

[0120] FLAT PAINT/FLEXBOND325/SYNTHETIC COALESCENT AID formulation (byweight) formulation (by volume) lb. gal. H2O 142.58 17.12 PG 43.53 5.03X-102 2.18 0.24 RM825 15.96 1.83 TAMOL850 18.18 1.84 WET260 4.88 0.56AMP95 2.18 0.28 TP-900 243.25 7.30 ATOMITE 195.91 8.68 FXBD325 435.3447.84 EG-DERIV (X1) 14.15 1.79 DREWPLUS 2.37 0.32 H2O 59.69 7.17 Total1180.18 100.00 wt/gal 11.80 % sol/wt 58.93 % sol/vol. 42.33 % PVC 37.76

[0121] Semigloss and flat paint formulations of low Tg vinyl acryliclatex, UCAR 379G, have been prepared for physical testing. Theformulations with TEXANOL® are given in the Tables below. GLOSSPAINT/UCAR379G/TEXANOL ® formulation (by weight) formulation (by volume)lb. gal. H2O 37.19 4.47 PG 72.80 8.42 X-102 2.01 0.22 RM825 17.08 1.96TAMOL850 7.89 0.80 WET260 4.53 0.52 AMP95 1.41 0.18 0.00 TP-900 226.026.79 ATOMITE 74.15 3.29 0.00 UCAR379 587.51 64.92 TEXANOL ® 33.45 4.23DREWPLUS 1.93 0.26 H2O 32.88 3.95 Total 1098.86 100.00 wt/gal 10.99 %sol/wt 57.95 % sol/vol. 44.91 % PVC 22.43

[0122] FLAT PAINT/UCAR379G/TEXANOL ® formulation (by weight) formulation(by volume) lb. gal. H2O 132.28 15.88 PG 54.86 6.34 X-102 2.21 0.25RM825 17.19 1.98 TAMOL850 18.47 1.87 WET260 4.98 0.58 AMP95 1.11 0.140.00 TP-900 248.28 7.46 ATOMITE 199.08 8.82 0.00 UCAR379 442.41 48.89TEXANOL ® 25.22 3.19 DREWPLUS 2.12 0.28 H2O 36.12 4.34 Total 1184.33100.00 wt/gal 11.84 % sol/wt 59.78 % sol/vol. 43.19 % PVC 37.68

[0123] The formulations with ethylene glycol soybean oil esters aregiven in the Tables below GLOSS PAINT/UCAR379G/SYNTHETIC COALESCENT AIDformulation (by weight) formulation (by volume) lb. gal. H2O 82.21 9.87PG 68.37 7.90 X-102 1.89 0.21 RM825 18.91 2.17 TAMOL850 7.94 0.80 WET2604.48 0.52 AMP95 1.32 0.17 0.00 TP-900 212.27 6.37 ATOMITE 69.63 3.090.00 UCAR379 551.76 60.97 EG DERIV (X1) 31.41 3.98 DREWPLUS 1.82 0.24H2O 30.88 3.71 Total 1082.90 100.00 wt/gal 10.83 % sol/wt 55.33 %sol/vol. 42.29 % PVC 22.37

[0124] FLAT PAINT/UCAR379G/SYNTHETIC COALESCENT AID formulation (byweight) formulation (by volume) lb. gal. H2O 133.08 15.98 PG 55.19 6.38X-102 2.23 0.25 RM825 11.57 1.33 TAMOL850 19.14 1.93 WET260 5.01 0.58AMP95 1.11 0.14 0.00 TP-900 249.77 7.50 ATOMITE 200.28 8.87 0.00 UCAR379445.07 49.18 EG DERIV (X1) 25.37 3.21 DREWPLUS 2.14 0.29 H2O 36.34 4.36Total 1186.29 100.00 Wt/gal 11.86 % sol/wt 59.94 % sol/vol. 43.32 % PVC37.80

[0125] Results

[0126] The physical property testing results are shown in the Tablebelow. FREEZE-THAW STABILITY AND THERMAL STABILITY TESTING ViscosityHiding physical (cps) power gloss @ 60° appearance gloss/ucar/ TEXANOL ®Control 1785 94.4 20.7/17 no settling Oven 1985 94.0 17.7/14.3 nosettling Freezer 1775 94.8 20.5/17.4 no settling gloss/flexbond/TEXANOL ® Control 1735 95.2 26.7/24.2 no settling Oven 1715 94.425.3/21.4 no settling Freezer 1570 95.4 27.8/24.2 no settling flat/ucar/TEXANOL ® Control 1345 95.8  3.6/3.4 no settling oven 1375 94.9  3.4/3.3no settling freezer 1260 95.0  3.5/3.3 no settling flat/flexbond/TEXANOL ® control 1965 94.2  4.5/4.9 no settling oven 1885 93.8  4.2/4.6no settling freezer 1505 94.3  4.6/4.8 no settling gloss/ucar/syntheticcoalescent aid Control 2005 93.9 21.0/17.7 no settling oven 1610 92.718.8/16.4 no settling freezer 2235 93.7 21.1/18.4 no settlinggloss/flexbond/ synthetic coalescent aid control 1170 95.3 26.8/23.6 nosettling oven 1170 94.4 25.3/20.7 no settling freezer 1120 95.126.8/22.6 no settling flat/ucar/synthetic coalescent aid control 198594.9  5.1/4.3 no settling oven 2135 94.1  4.7/4.0 no settling freezer1870 93.9  4.8/4.2 no settling flat/flexbond/ synthetic coalescent aidcontrol 1580 94.2  5.4/5.2 no settling oven 1540 93.8  4.7/4.8 nosettling freezer 1390 94.7  5.4/5.3 no settling

[0127] The incorporation of ethylene glycol soy oil ester as acoalescent aid in paint formulations with low Tg latex polymersexhibited thermal stability and freeze-thaw stability similar tocommercial coalescent aid, TEXANOL® (Eastman Kodak). There was nosettling in all paint formulations. The gloss and hiding power werestable in all paint formulation after freeze-thaw and heat-cool for atleast 5 cycles. SCRUB RESISTANCE TESTING RESULTS Scrub resistant(cycles)gloss/ucar/TEXANOL ® >3000 gloss/flexbond/TEXANOL ® >3000flat/ucar/TEXANOL ® >3000 flat/flexbond/TEXANOL ® >3000gloss/ucar/synthetic coalescent aid >3000 gloss/flexbond/syntheticcoalescent aid >3000 flat/ucar/synthetic coalescent aid >3000flat/flexbond/synthetic coalescent aid >3000

[0128] The scrub resistance of paint formulations formulated withethylene glycol soy oil ester as a coalescent aid showed an excellentscrub resistance similar to paint formulations with commercialcoalescent aid, TEXANOL® (Eastman Kodak). Both of low Tg latex polymersused in this invention gave the same result in scrub resistance.BLOCKING RESISTANCE TESTING RESULTS Blocking resistant ratingPerformance SEMIGLOSS Flexbond325 + TEXANOL ® 2.0 25-50% sealFlexbond325 + Methyl Ester 3.0-4.0 Poor-fair Flexbond325 + EG-derivative6.0-7.0 Good-very good Ucar379g + TEXANOL ® 3.0-4.0 Poor-fair Ucar379g +Methyl Ester 3.0 Poor Ucar379g + EG-derivative 5.0 Fair FLATFlexbond325 + TEXANOL ® 7.0 Good-very good Flexbond325 + Methyl Ester5.0-6.0 Fair-good Flexbond325 + EG-derivative 6.0 Good Ucar379g +TEXANOL ® 7.0-8.0 Good-very good Ucar379g + Methyl Ester 6.0-7.0 GoodUcar379g + EG-derivative 4.0-5.0 Fair

[0129] Semigloss paint formulation with ethylene glycol soy oil ester asa coalescent aid showed better blocking resistance than paintformulation with comparative coalescent aid, TEXANOL® (Eastman Kodak).Flat paint formulation with ethylene glycol soy oil ester as acoalescent aid showed poorer blocking resistance than paint formulationwith comparative coalescent aid, TEXANOL® (Eastman Kodak). Both low Tglatex polymers used in this invention provided the same trend ofblocking resistance performance. PENCIL HARDNESS TEST RESULTS Hardnessrating GLOSS Flexbond325 + TEXANOL ® 5B Flexbond325 + X1 5B-6Bucar379g + TEXANOL ® 6B ucar379g + X1 OVER 6B FLAT Flexbond325 +TEXANOL ® 4B Flexbond325 + X1 4B-5B ucar379g + TEXANOL ® 5B-6Bucar319g + X1 6B

[0130] Hardness of film from paint formulation with ethylene glycol soyoil ester as a coalescent aid was lower in hardness than the film frompaint formulated with the commercial coalescent aid, TEXANOL® (EastmanKodak). Both of low Tg latex polymers used in this invention providedless hardness with the new coalescent aid. ADHESION TEST RESULTS Surfaceof cross-cut area from which flaking has occurred on scratched panelwith epoxy primer GLOSS Flexbond325 + TEXANOL ® >65% >65% Flexbond325 +me-ester >65% >65% Flexbond325 + X1 >65% >65% Ucar379g +TEXANOL ® >65% >65% Ucar379g + Me-ester >65% >65% ucar379g +X1 >65% >65% FLAT Flexbond325 + TEXANOL ® >65% >65% Flexbond325 +me-ester >65% >65% Flexbond325 + X1 >65% >65% Ucar379g +TEXANOL ® >65% >65% Ucar379g + Me-ester >65% >65% Ucar379g + X1 >65%>65%

[0131] The semigloss and flat paint formulation, with both low Tg latexpolymers and ethylene glycol soy oil ester as a coalescent aid,exhibited poor performance in adhesion of paint film both on scratchedaluminum panel and on epoxy-primed aluminum panel. The same poorperformance occurred with commercial coalescent aid, TEXANOL® (EastmanKodak).

Example 4

[0132] Physical properties of paint formulations with a high Tg latexpolymer with ethylene glycol soybean oil esters and TEXANOL®. Only theethylene glycol soy oil ester derivative has been incorporated into apaint formulation for physical testing relative to the commercialcoalescent aids, TEXANOL® (a commercial coalescent aid), and EB.

[0133] Semigloss paint formulation of high Tg acrylic latex, ACRONALA846, has been prepared for physical testing. The formulations withTEXANOL® are given in the Table below. ACRONAL846/TEXANOL ® Formulation(by weight) formulation (by volume) lb. gal. H2O 75.18 9.03 PG 63.057.29 X-102 6.57 0.73 RM825 16.05 1.84 TAMOL850 2.41 0.24 WET KL245 12.811.48 AMP95 0.14 0.02 TP-900 169.75 5.10 ATOMITE 98.76 4.38 ACRONAL A846540.11 61.73 TEXANOL ® 27.07 3.43 DREWPLUS L493 5.25 0.70 H2O 33.64 4.04Total 1050.79 100.00 wt/gal 10.51 % sol/wt 53.62 % sol/vol. 41.88 % PVC22.62

[0134] The formulations with ethylene glycol soybean oil esters aregiven in the Table below. ACRONAL846/EG Formulation (by weight)formulation (by volume) lb. gal. H2O 75.57 9.07 PG 63.38 7.33 X-102 6.610.74 RM825 11.48 1.32 TAMOL850 2.42 0.24 WET KL245 12.87 1.49 AMP95 0.140.02 TP-900 170.63 5.12 ATOMITE 99.27 4.40 ACRONAL A846 542.91 62.05EG-derivative 27.21 3.46 DREWPLUS L493 5.27 0.70 H2O 33.82 4.06 Total1051.58 100.00 wt/gal 10.52 % sol/wt 56.34 % sol/vol. 45.44 % PVC 20.95

[0135] Semigloss paint formulation of high Tg PS/PMMA latex, UCAR 430,has been prepared for physical testing. The formulations with ethyleneglycol soybean oil esters or TEXANOL® are given in the Tables below.UCAR430/TEXANOL ® Formulation (by weight) formulation (by volume) lb.gal. H2O 79.51 9.55 PG 55.69 6.44 X-102 6.71 0.75 RM825 22.32 2.57TAMOL850 3.05 0.31 WET KL245 9.67 1.12 AMP95 0.28 0.04 TP-900 162.604.88 ATOMITE 89.43 3.96 UCAR430 548.78 63.08 TEXANOL ® 36.99 4.68DREWPLUS L493 2.56 0.34 H2O 19.11 2.29 1036.70 100.00 wt/gal 10.37 %sol/wt 50.38 % sol/vol. 38.62 % PVC 22.90

[0136] UCAR430/EG formulation (by weight) formulation (by volume) lb.gal H2O 80.01 9.61 PG 56.04 6.48 X-102 6.75 0.75 RM825 17.51 2.01TAMOL850 3.07 0.31 WET KL245 9.74 1.13 AMP95 0.29 0.04 TP-900 163.624.91 ATOMITE 89.99 3.99 UCAR430 552.22 63.47 EG-derivative 37.22 4.74DREWPLUS L493 1.96 0.26 H2O 19.23 2.31 1037.64 100.00 wt/gal 10.38 %sol/wt 54.10 % sol/vol. 43.44 % PVC 20.49

[0137] Results

[0138] The physical property testing results are shown in Table below.FREEZE-THAW AND THERMAL STABILITIES Semigloss high hiding physical Tglatex power gloss @ 60° appearance Ucar 430 + TEXANOL ® Control 9226.6/21.1 no settling Oven 90 21.0/17.0 no settling Freezer 91.526.6/21.2 no settling Ucar 430 + EG-derivative Control 93 33.9/25.9 nosettling Oven 92 33.1/24.2 no settling Freezer 93 33.0/26.6 no settlingAcronal A846 + TEXANOL ® Control 94 29.5/23.3 no settling Oven 9531.2/24.8 no settling Freezer 94 29.1/28.4 no settling Acronal A846 +EG-derivative Control 94 34.6/26.1 no settling Oven 95 35.3/18.7 nosettling Freezer 95 34.8/24.5 no settling

[0139] From the results, the incorporation of ethylene glycol soy oilester as a coalescent aid in paint formulations with high Tg latexpolymers showed thermal stability and freeze-thaw stability similar tocommercial coalescent aid, TEXANOL® (Eastman Kodak). There was nosettling in all paint formulations. The gloss and hiding power werestable in all paint formulation after freeze-thaw and heat-cool for atleast 5 cycles. Paint formulation with the new coalescent aid manifestedthe improvement in gloss relatively to conventional coalescent aidincorporated formulation. SCRUB RESISTANCE TESTING RESULTS Semiglosspaint Scrub resistance (cycles) Acronal A846 + TEXANOL ® 748 AcronalA846 + Methyl Ester 782 Acronal A846 + EG-derivative 995 Ucar 430 +TEXANOL ® 687 Ucar 430 + Methyl Ester 755 Ucar 430 + EG-derivative 783

[0140] The scrub resistance of paint formulation with ethylene glycolsoy oil ester as a coalescent aid show better scrub resistance thanpaint formulation with commercial coalescent aid, TEXANOL® (EastmanKodak). Both of high Tg latex polymers used in this invention gave thesame trend in scrub resistance. BLOCKING RESISTANCE TESTING RESULTSBlocking resistance rating Performance Acronal A846 + TEXANOL ® 5.0-6.0Fair-good Acronal A846 + Methyl Ester 5.0-6.0 Fair-good Acronal A846 +EG-derivative 6.0-7.0 Good-very good Ucar 430 + TEXANOL ® 8.0 Very goodUcar 430 + Methyl Ester 8.0 Very good Ucar 430 + EG-derivative 9.0Excellent

[0141] Paint formulation with ethylene glycol soy oil ester as acoalescent aid showed better blocking resistance than paint formulationwith the commercial coalescent aid, TEXANOL® (Eastman Kodak). Both ofhigh Tg latex polymers used in this invention provided good blockingresistance. PENCIL HARDNESS TEST RESULTS Semigloss paint Hardness ratingAcronal A846 + TEXANOL ® 2B Acronal A846 + Methyl Ester 2B AcronalA846 + EG-derivative 3B Ucar 430 + TEXANOL ® 4B Ucar 430 + Methyl Ester4B Ucar 430 + EG-derivative 5B

[0142] Hardness of film from paint formulation with ethylene glycol soyoil ester as a coalescent aid was lower than hardness of film from paintformulation with the commercial coalescent aid, TEXANOL® (EastmanKodak). Both of high Tg latex polymers used in this invention providedless hardness. ADHESION TEST Surface of cross-cut area from whichflaking Semigloss high Tg latex has occurred (with epoxy primer) AcronalA846 + TEXANOL ® >65% Acronal A846 + Methyl Ester >65% Acronal A846 +EG-derivative >65% Ucar 430 + TEXANOL ® >65% Ucar 430 + MethylEster >65% Ucar 430 + EG-derivative >65%

[0143] Paint formulation with both high Tg latex polymers and ethyleneglycol soy oil ester as a coalescent aid, exhibited poor performance inadhesion of paint film on epoxy-primed aluminum panel. The same poorperformance occurred with the commercial coalescent aid, TEXANOL®(Eastman Kodak).

Example 5

[0144] Evaporation rate of new glycol derivative soy oil esterrelatively to conventional coalescent aids, TEXANOL® (Eastman Kodak) andEthylene glycol n-Butyl ether (Union Carbide).

[0145] Weighed three replicas of each coalescent aid into aluminum pans.Keep all aluminum pans with coalescent at room temperature. Thepercentage of weight loss of each coalescent aid was measured.

[0146] The evaporation rate of ethylene glycol, propylene glycol andmethyl ester derivatives as well as TEXANOL® (Eastman Kodak) andEthylene glycol n-Butyl ether (EB, Union Carbide) are shown below inFIG. 5.

[0147] The evaporation rates of glycol derivative and methyl soy oilester are lower than comparative coalescent aids (TEXANOL® and EB).Ethylene glycol monobutyl ether is water-soluble coalescent aid andevaporate from the film and is therefore a VOC. TEXANOL®,water-insoluble coalescent aid could gradually evaporate from the filmwhile it is aging. The new soy oil glycol ester in this invention doesnot show a loss in weight. This means new soy oil glycol ester wouldbecome a part of coating film, and does not give off VOCs. The dataindicates a slight but real increase in weight after 2 days consistentwith a drying oil reacting slowly with air to cure.

[0148] MFFT Measurement with the Incorporation of Glycol Palmitate,Oleate and Linoleate.

[0149] Ethylene glycol derivatives of palmitic acid, oleic acid andlinoleic acid were added to coatings formulated with high Tg resin (Ucar430 and Acronal A846) at levels of 0.5%, 0.75% and 1.0% by weight. Theformulations were equilibrated for two days before taking MFFTmeasurement.

[0150] The MFFT results are shown in FIGS. 6-9.

[0151] UCAR 430

[0152] The results from the MFFT measurements of high Tg resin (UCAR430, PS/PMMA) formulation are shown in FIGS. 6 and 7. As FIGS. 6 and 7illustrate, it was found that glycol fatty acid ester and glycol soy oilester could lower the minimum film formation temperature better thanethylene glycol monobutyl ether (EB). This may be due to the slowevaporation rates of the glycol fatty acid ester and glycol soy oilester relative to ethylene glycol monobutyl ether. Thus the coalescentnew aids may stay in the system long enough to function in lowering theminimum film formation temperature. As shown in FIG. 7, all glycol soyoil esters could reduce the minimum film formation temperature in thesame fashion as commercial coalescent aid, TEXANOL®.

[0153] Some of glycol fatty acid esters, i.e. methyl soyate, ethyleneglycol oleate and ethylene glycol linoleate, could lower the minimumfilm formation temperature better than TEXANOL®. Methyl soyate estercould lower the MFFT the best.

[0154] ACRONAL A846

[0155] The MFFT results of high Tg resin (ACRONAL A846, pure acrylicresin) formulation, it was found that all glycol fatty acid ester andglycol soy oil esters could lower the minimum film formation temperaturebetter than ethylene glycol monobutyl ether (EB). They also could reducethe minimum film formation temperature in the same manner as commercialcoalescent aid, TEXANOL®. None of them could lower the minimum filmformation temperature better than TEXANOL® except ethylene glycol soyoil ester at concentration of 1.0% by weight.

Example 6

[0156] AC Impedence measurements were taken to obtain the trend of thecoating capacitance and coating resistance values as a function of drytime to express the film formation of latex coating as a function of drytime. In addition, the measurements with various coalescent aidformulations would also impact the effect of coalescent aid in latexfilm formation.

[0157] AC Impedence measurements were taken on 0.5% EB as a function ofdry time, 0.5% TEXANOL® as a function of dry time, and 0.5% ethyleneglycol soy oil ester as a function of dry time. A two-time constantequivalent circuit model, as a hypothetical equivalent circuit for thecoated aluminum system, was used to correlate the Bolt and Nyquistresult plots from the AC Impedence measurements. The coating resistance,coating capacitance, charge transfer resistance, and associated doublelayer capacitance obtained were plotted as a function of dry time.

[0158] As FIG. 10 illustrates, the coating resistance increased as afunction of dry time until approximately 8 hours dry time, then itleveled off. For the charge transfer resistance, there was a slightincrease in the resistance which was not significant. This was becausethere was no corrosion taking place.

[0159] The coating capacitance plot (shown in FIG. 11) exhibited adecreasing trend as a function of dry time until approximately 8 hoursthen the capacitance was constant. This trend can be explained by thephenomenon that at shorter drying periods, the coating film was notcompletely coalesced, and there remained pores and the diffusion ofelectrolyte solution through the film could take place which resulted inthe increase in film capacitance. For the longer drying periods the filmwas more coalesced and less diffusion took place. Therefore, theresistance of film is higher and the capacitance was lower as a functionof longer dry periods.

[0160] As FIGS. 10 and 11 illustrate, the AC Impedance measurementsshowed an increase in coating resistance and a decrease in coatingcapacitance as well as the formulation with the conventional coalescentaid, TEXANOL®. This supported the contention that sobean oil coalescentaid effected latex film formation as well as TEXANOL®.

Example 7

[0161] Various IR and NMR spectra were taken of glycol soybean oil esterderivatives, methyl soybean oil derivatives, and ethylene glycol fattyacid derivatives.

[0162] IR-Spectra

[0163] Infrared spectra of soybean oil and soybean oil ester derivativesare shown in FIGS. 12-19. FIG. 12 shows the IR spectrum of soybean oil.FIGS. 13-17 show the IR spectra of the soybean oil ester derivatives ofethylene glycol (FIG. 13), propylene glycol (FIG. 14), diethylene glycol(FIG. 15), dipropylene glycol (FIG. 16) and the methyl soybean oil esterderivative (FIG. 17). FIG. 18 shows the IR spectrum of the ethyleneglycol oleate ester derivative and FIG. 19 shows the IR spectrum of theethylene glycol linoleate ester derivative.

[0164]¹H-NMR Data

[0165]¹H-NMR spectra were obtained for soybean oil and soybean oil esterderivatives. FIG. 20 shows the ¹H-NMR spectrum of soybean oil. FIGS.21-25 show the ¹H-NMR spectra of the soybean oil ester derivatives ofethylene glycol (FIG. 21), propylene glycol (FIG. 22), diethylene glycol(FIG. 23), dipropylene glycol (FIG. 24) and the methyl soybean oil esterderivative (FIG. 25). The ¹H-NMR spectrum of the ethylene glycol oleateester derivative is shown in FIG. 26, and FIG. 27 shows the ¹H-NMRspectrum of the ethylene glycol linoleate ester derivative.

[0166]¹³C-NMR Data

[0167]¹³C-NMR DATA spectra were obtained for soybean oil and soybean oilester derivatives. FIG. 28 shows the ¹³C-NMR DATA spectrum of soybeanoil. FIGS. 29-32 show the ¹³C-NMR DATA spectra of the soybean oil esterderivatives of ethylene glycol (FIG. 29), propylene glycol (FIG. 30),diethylene glycol (FIG. 31), and dipropylene glycol (FIG. 32).

Example 8

[0168] Physical properties such as solubility parameters, HydrophilicLipophilic Balance values (HLB values), density, and surface tensionwere measured of various soybean oil esters, ethylene glycol monobutylether (EB), and TEXANOL®. The soybean oil esters included ethyleneglycol soybean oil derivative, diethylene glycol soybean oil derivative,propylene glycol soybean oil derivative, dipropylene glycol soybean oilderivative, and methyl ester soybean oil derivative. Soy oil derivativeesters EG^(a) DEG^(b) PG^(c) DPG^(d) ME^(e) EB^(f) TEXANOL ®^(g)Properties Density 0.94 0.93 0.91 0.91 0.87 (g/cm³) HLB 2.7 4.8 3.4 5.9N/A 14.9 N/A Interfacial 36.2 36.1 33.3 35.7 30.1 27.4 28.9 tension(dyne/cm) Solubility Para- meters δ_(total) 18.6 18.2 18.0 17.6 17.920.7 19.3 (J/cm³)^(1/2) δ_(d) 16.2 15.8 15.7 15.4 17.2 15.9 15.6(J/cm³)^(1/2) δ_(p) 2.03 2.04 1.88 1.85 1.50 4.9 3.07 (J/cm³)^(1/2)δ_(h) 8.8 8.7 8.5 8.3 4.6 12.3 10.9 (J/cm³)^(1/2)

[0169] From the solubility parameters shown in the table above, it wasfound that the total solubility parameter of EB is greater than TEXANOL®and the glycol soybean oil derivatives. In addition, the polarsolubility parameter (δ_(p)) and hydrogen bonding solubility parameter(δ_(h)) decreased in the order of EB>TEXANOL®>glycol soybean oilderivatives. Therefore, EB would be able to be miscible with waterbetter than TEXANOL® and glycol soybean oil derivatives.

[0170] The solubility parameter of a polymer, the polystyrene methylmethacrylate copolymer (PS-MMA, UCAR 430) was considered. The solubilityparameter of PS-MMA is 18.2 (J/cm3)½ as stated in J. Brandrup and E. H.Immergut, Polymer Handbook, 2^(nd) ed., Wiley-lnterscience, New York, p519 (1989). It was found that the solubility parameter of glycol soy oilesters and TEXANOL® were close to that of polystyrene rather than EB.Ideally for hydrophobic coalescent aids, a solubility parameter matchwill produce a better coalescent aid. As a result, TEXANOL® and glycolsoybean oil derivatives should coalesce the polystyrene methylmethacrylate copolymer (UCAR 430) better than EB.

[0171] Higher HLB values correspond with greater miscibility with water.In the above table the HLB value of EB was greater than that of glycolsoybean oil derivatives. This corresponded with the solubility parameterof EB. Therefore, EB would be miscible with water better than glycolsoybean oil derivatives.

[0172] The value of the interfacial tension is a measure of thedissimilarity of the two types of molecules facing each other across theinterface. The smaller the interfacial tension, the more similar innature the two molecules are, and the greater the interaction betweenthe molecules. In the table above the interfacial tension of EB was 27.4dyne/cm which was less than those of TEXANOL® and glycol soybean oilesters. Therefore, EB would be miscible with water better than TEXANOL®and glycol soybean oil esters.

What is claimed is:
 1. A film-forming composition comprising acontinuous aqueous phase and a dispersed phase, the dispersed phasecomprising (i) a particulate polymer or emulsified liquid prepolymer,and (ii) a coalescent aid comprising an ester having the formula RCOOXwherein R and X are independently hydrocarbyl or substituted hydrocarbyland at least one of R and X comprises at least two unsaturatedcarbon-carbon bonds.
 2. The film-forming composition of claim 1 whereinR and X independently comprise about 1 to about 30 carbon atoms.
 3. Thefilm-forming composition of claim 1 wherein R and X independentlycomprise about 1 to about 30 carbon atoms and, in combination, containno more than about 35 carbon atoms.
 4. The film-forming composition ofclaim 1 wherein R and X each contain an unsaturated carbon-carbon bond.5. The film-forming composition of claim 1 wherein R comprises at leasttwo unsaturated carbon-carbon bonds in conjugation.
 6. The film-formingcomposition of claim 1 wherein R or X is substituted hydrocarbyl and thehydrocarbyl substituent is selected from the group consisting ofketones, esters, alcohols, amides, halogens, urea, urethane, and nitrilesubstituents.
 7. The film-forming composition of claim 1 wherein theester is prepared by the transesterification reaction between a fattyacid and a glycol.
 8. The film-forming composition of claim 1 whereinthe ester is an ester derived from a fatty acid of soybean oil, canolaoil, or linseed oil.
 9. The film-forming composition of claim 1 whereinthe ester is an ethylene glycol monoester derived from a fatty acid ofsoybean oil.
 10. The film-forming composition of claim 1 wherein theester is an diethylene glycol monoester derived from a fatty acid ofsoybean oil.
 11. The film-forming composition of claim 1 wherein theester is a propylene glycol monoester derived from a fatty acid ofsoybean oil.
 12. The film-forming composition of claim 1 wherein theester is a dipropylene glycol monoester derived from a fatty acid ofsoybean oil.
 13. The film-forming composition of claim 1 wherein theester is a methyl ester derived from a fatty acid of soybean oil. 14.The film-forming composition of claim 7 wherein the fatty acid is afatty acid derived from soybean oil.
 15. The film-forming composition ofclaim 1 wherein the weight of the ester is about 0.1% to about 50% ofthe weight of the particulate polymer or liquid pre-polymer.
 16. Thefilm-forming composition of claim 1 wherein the weight of the ester isabout 0.1% to about 4% of the weight of the particulate polymer orliquid pre-polymer.
 17. The film-forming composition of claim 1 whereinthe continuous aqueous phase constitutes at least about 20 wt. % of thefilm-forming composition.
 18. The film-forming composition of claim 17wherein the ester is an ester derived from a fatty acid of soybean oil,canola oil, or linseed oil.
 19. The film-forming composition of claim 1wherein the dispersed or continuous aqueous phase further comprises anadditive selected from the group consisting of wetting aids,dispersants, thickeners, defoaming agents, biocides, algicides,ultra-violet inhibitors, flow agents, levelling agents, reologymodifiers, freeze thaw stabilizing agents, pH modifiers, flash rustinhibitors, and biocides.
 20. The film-forming composition of claim 1wherein the film-forming composition comprises a mixture of coalescentaids and the ester comprises at least about 5 wt. % of the mixture. 21.The film-forming composition of claim 1 wherein the ester is derivedfrom a fatty acid contained in an oil obtained from a plant or animaland the unsaturated fatty acid comprises at least about 25 wt. % of thefatty acid content of the oil.
 22. The film-forming composition of claim1 wherein the film-forming composition comprises a mixture of coalescentaids, the ester comprises at least about 5 wt. % of the mixture, theester is derived from a fatty acid contained in an oil obtained from aplant or animal, and the unsaturated fatty acid comprises at least about25 wt. % of the fatty acid content of the oil.
 23. The film-formingcomposition of claim 1 wherein the film-forming composition comprises amixture of coalescent aids, the ester comprises at least about 5 wt. %of the mixture, the ester is derived from a fatty acid contained in anoil obtained from a plant or animal, and the unsaturated fatty acidcomprises at least about 50 wt. % of the fatty acid content of the oil.24. The film-forming composition of claim 23 wherein the film-formingcomposition contains at least about 20 wt. % water.
 25. The film-formingcomposition of claim 23 wherein the film-forming composition contains atleast about 20 wt. % water, at least about 10 wt. % particulate polymeror liquid pre-polymer, and the weight of the ester is about 0.1% toabout 50% of the weight of the particulate polymer or liquidpre-polymer.
 26. The film-forming composition of claim 1 wherein thefilm-forming composition contains at least about 20 wt. % water, atleast about 10 wt. % particulate polymer or liquid pre-polymer, and theweight of the ester is about 0.1% to about 50% of the weight of theparticulate polymer or liquid pre-polymer.
 27. The film-formingcomposition of claim 26 wherein at least 95 wt. % of the ester isdissolved in the particulate polymer or liquid pre-polymer.
 28. Thefilm-forming composition of claim 1 wherein at least 95 wt. % of theester is dissolved in the particulate polymer or liquid pre-polymer. 29.The film-forming composition of claim 1 wherein the continuous aqueousphase contains less than about 10 wt. % organic solvent.
 30. Thefilm-forming composition of claim 1 wherein at least 95 wt. % of theester is dissolved in the particulate polymer or liquid pre-polymer andthe continuous aqueous phase contains less than about 10 wt. % organicsolvent.
 31. The film-forming composition of claim 30 wherein thefilm-forming composition contains at least about 20 wt. % water, atleast about 10 wt. % particulate polymer or liquid pre-polymer, and theweight of the ester is about 0.1% to about 50% of the weight of theparticulate polymer or liquid pre-polymer.
 32. The film-formingcomposition of claim 31 wherein the film-forming composition comprises amixture of coalescent aids, the ester comprises at least about 5 wt. %of the mixture, the ester is derived from a fatty acid contained in anoil found in a plant or animal, and the unsaturated fatty acid comprisesat least about 50 wt. % of the fatty acid content of the oil.
 33. Thefilm-forming composition of claim 30 wherein the film-formingcomposition comprises a mixture of coalescent aids, the ester comprisesat least about 5 wt. % of the mixture, the ester is derived from a fattyacid contained in an oil found in a plant or animal, and the unsaturatedfatty acid comprises at least about 50 wt. % of the fatty acid contentof the oil.
 34. A film-forming composition comprising at least about 10wt. % of a continuous aqueous phase and a dispersed phase, the dispersedphase comprising (i) a particulate polymer or emulsified liquidprepolymer, and (ii) a coalescent aid comprising an ester derived from afatty acid contained in an oil found in a plant or animal, the esterhaving the formula RCOOX wherein R and X are independently hydrocarbylor substituted hydrocarbyl and at least one of R and X comprises atleast two unsaturated carbon-carbon bonds.
 35. The film-formingcomposition of claim 34 wherein at least 95 wt. % of the ester isdissolved in the particulate polymer or liquid pre-polymer and thecontinuous aqueous phase contains less than about 10 wt. % organicsolvent, based upon the weight of the continuous phase.
 36. Thefilm-forming composition of claim 35 wherein the film-formingcomposition contains at least about 20 wt. % water, at least about 10wt. % particulate polymer or liquid pre-polymer, and the weight of theester is about 0.1% to about 50% of the weight of the particulatepolymer or liquid pre-polymer.
 37. The film-forming composition of claim35 wherein the film-forming composition comprises a mixture ofcoalescent aids, the ester comprises at least about 5 wt. % of themixture, the ester is derived from a fatty acid contained in an oilfound in a plant or animal, and the unsaturated fatty acid comprises atleast about 50 wt. % of the fatty acid content of the oil.
 38. Thefilm-forming composition of claim 34 wherein the film-formingcomposition comprises a mixture of coalescent aids, the ester comprisesat least about 5 wt. % of the mixture, the ester is derived from a fattyacid contained in an oil found in a plant or animal, and the unsaturatedfatty acid comprises at least about 50 wt. % of the fatty acid contentof the oil.